EP0523838B9 - Verfahren zur Isomerisierung von geradlinigen Olefinen in Isoolefine - Google Patents

Verfahren zur Isomerisierung von geradlinigen Olefinen in Isoolefine Download PDF

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EP0523838B9
EP0523838B9 EP92305090A EP92305090A EP0523838B9 EP 0523838 B9 EP0523838 B9 EP 0523838B9 EP 92305090 A EP92305090 A EP 92305090A EP 92305090 A EP92305090 A EP 92305090A EP 0523838 B9 EP0523838 B9 EP 0523838B9
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hrs
butene
catalyst
feed
eff
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French (fr)
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EP0523838A3 (en
EP0523838A2 (de
EP0523838B1 (de
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Donald H. Powers
Brendan D. Murray
Bruce H.C. Winquist
Edwin M. Callender
James H. Varner
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Equistar Chemicals LP
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Equistar Chemicals LP
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
    • C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/82—Phosphates
    • B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
    • B01J29/85—Silicoaluminophosphates [SAPO compounds]
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
    • C07C5/2767—Changing the number of side-chains
    • C07C5/277—Catalytic processes
    • C07C5/2775—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65

Definitions

  • This invention relates to structural isomerization of linear olefins to methyl branched isoolefins using zeolite compositions as isomerizing catalysts.
  • an alkene such as normal butene
  • a methyl branched alkene for example isobutylene
  • Such converted isoalkenes then can be reacted further, such as by polymerization or oxidation, to form useful products.
  • Normal alkenes containing four carbon atoms (1-butene, trans-2-butene and cis-2-butene) and five carbon atoms (1-pentene, trans-2-pentene, and cis-2-pentene) are relatively inexpensive starting compounds.
  • butenes and amylenes, including to a minor extent isobutylene and isoamylene are obtained as a by-product from refinery and petrochemical processes such as catalytic and thermal cracking units.
  • Zeolite materials both natural and synthetic, are known to have catalytic properties for many hydrocarbon processes.
  • Zeolites typically are ordered porous crystalline aluminosilicates having a definite structure with cavities interconnected by channels. The cavities and channels throughout the crystalline material generally can be of such a size to allow selective separation of hydrocarbons.
  • Such a hydrocarbon separation by the crystalline aluminosilicates essentially depends on discrimination between molecular dimensions. Consequently, these materials in many instances are known in the art as "molecular sieves" and are used, in addition to catalytic properties, for certain selective adsorptive processes.
  • Zeolite molecular sieves are discussed in great detail in D.W. Breck, Zeolite Molecular Sieves, Robert E. Krieger Publishing Company, Malabar, Florida (1984).
  • zeolite includes a wide variety of both natural and synthetic positive ion-containing crystalline aluminosilicate materials, including molecular sieves. They generally are characterized as crystalline aluminosilicates which comprise networks of SiO 4 and AlO 4 tetrahedra in which silicon and aluminum atoms are cross-linked in a three-dimensional framework by sharing of oxygen atoms. This framework structure contains channels or interconnected voids that are occupied by cations, such as sodium, potassium, ammonium, hydrogen, magnesium, calcium, and water molecules. The water may be removed reversibly, such as by heating, which leaves a crystalline host structure available for catalytic activity.
  • zeolite in this specification is not limited to crystalline aluminosilicates.
  • the term as used herein also includes silicoaluminophosphates (SAPO), metal integrated aluminophosphates (MeAPO and ELAPO), metal integrated silicoaluminophosphates (MeAPSO and ELAPSO).
  • SAPO silicoaluminophosphates
  • MeAPO and ELAPO metal integrated aluminophosphates
  • MeAPSO and ELAPSO metal integrated silicoaluminophosphates
  • the MeAPO, MeAPSO, ELAPO, and ELAPSO families have additional elements included in their framework.
  • Me represents the elements Co, Fe, Mg, Mn, or Zn
  • El represents the elements Li, Be, Ga, Ge, As, or Ti.
  • An alternative definition would be "zeolitic type molecular sieve" to encompass the materials useful for this invention.
  • Zeolites have been specifically named and described as Zeolite A (U.S. Patent No. 2,882,243), Zeolite X (U.S. Patent No. 2,882,244), Zeolite Y (U.S. Patent No. 3,130,007), Zeolite ZSM-5 (U.S. Patent No. 3,702,886), Zeolite ZSM-11 (U.S. Patent No. 3,709,979), Zeolite ZSM-12 (U.S. Patent No.
  • EP-A-0 111 808 discloses an isomerisation catalyst formed from a zeolite of the pentasil family such as ZSM-12 and a kaolinite-containing clay mineral.
  • catalysts for structurally isomerizing alkenes particularly butene to isobutene
  • an associated catalytic metal such as platinum, palladium, boron or gallium.
  • a linear olefin is converted under isomerizing conditions to a methyl branched olefin using an isomerizing catalyst composition made up of a zeolite having only in one dimension a pore structure having a pore size small enough to retard by-products and retard the formation of coke and its precursors and large enough to permit entry of the linear olefin and diffusion of the isoolefin product.
  • an isomerizing catalyst composition made up of a zeolite having only in one dimension a pore structure having a pore size small enough to retard by-products and retard the formation of coke and its precursors and large enough to permit entry of the linear olefin and diffusion of the isoolefin product.
  • Such zeolites have in one dimension a pore structure with a pore size ranging from more than 0.42 nm to less than 0.7 nm .
  • Zeolites with this specified pore size are typically referred to as medium or intermediate pore zeolites and typically have a 10-member (or puckered 12-member) ring channel structure in one dimension and an 8-member or less (small pore) in the other dimensions, if any.
  • a one-dimensional pore structure is considered one in which the channels having the desired pore size do not interconnect with other channels of similar or larger dimensions; it may also be considered alternatively as a channel pore structure ( see U.S. Patent No. 3,864,283) or uni-directional sieve.
  • Such one-dimensional, intermediate pore size catalyst compositions provide increased selectivity of the isomerization reaction, decreased dimer and trimer by-product formation, and decreased coking of the catalyst.
  • Zeolites that contain small pores do not allow for diffusion of the methyl branched isoolefin product, e.g., isobutylene; while zeolites that contain large pores (i.e., greater than about 0.7 nm) in any one dimension are subject to substantial by-product formation and coking. Coking is believed to be the result of oligmerization and polymerization, aromatization, or alkylation of the feed paraffin or olefin hydrocarbons. Zeolites of this invention should contain at least one pore dimension with the specified pore size. A two or three-dimensional pore structure having the specified pore size would permit substantial contact of the isomerizing olefins and thereby facilitate unwanted dimerization and trimerization reactions.
  • the processes of this invention are characterized by selectivities which range from 50% to 99% over run lengths of 48 to 120 hours, and isoolefin yields of between 25% to 40% at the beginning of a run and 12% to 40% at the end of run conditions. Under preferred conditions with temperatures at least 370°C, selectivities generally exceed 70% over run lengths of 48 to 120 hours.
  • a process for structurally isomerising a C 4 to C 10 linear olefin to a methyl branched isoolefin which comprises contacting said olefin with a catalyst comprising the hydrogen form of ferrierite or an isotypic structure thereof, having a silica/alumina ratio from 42:1 to 300:1, at isomerisation conditions comprising a temperature from 340° to 600°, an olefin partial pressure above 0.5 atmosphere (50.66 kPa), and a hydrocarbon weight hour space velocity from 1 to 50 hr -1 .
  • the hydrocarbon feed useful for this invention comprises a substantially linear alkene.
  • the linear alkene contains four to ten carbon atoms. More than one such alkene can be present in the feed.
  • Also considered a linear alkene for purposes of this invention is a compound containing a linear alkene segment with four to ten carbon atoms. It is believed that long chain linear alkenes and compounds containing long chain linear segments may penetrate the zeolite catalyst for a distance effective to allow isomerization. Thus, the entire molecule need not be small enough to fit entirely within the pore structure of the catalyst.
  • the preferred feed contains butylene or amylene.
  • n-butylene includes all forms of n-butylene, for example 1-butene and 2-butene, either trans-2-butene or cis-2-butene, and mixtures thereof.
  • n-amylene or n-pentene includes 1-pentene, cis- or trans-2-pentene, or mixtures thereof.
  • the n-butylene or n-amylene used in the processes of this invention is generally in the presence of other substances such as other hydrocarbons.
  • a feedstream used in the process of the invention containing n-butylene or n-amylene also can contain other hydrocarbons such as alkanes, other olefins, aromatics, hydrogen, and inert gases.
  • the n-butene feedstream used in this invention contains 40 to 100 wt.% n-butene.
  • a hydrocarbon feedstream from a fluid catalytic cracking effluent stream generally contains 40 to 60 wt.% normal butene and a hydrocarbon effluent from an ether processing unit, such as a methyl-tert-butyl ether (MTBE) processing unit generally containing from 40 to 100 wt.% n-butylene.
  • MTBE methyl-tert-butyl ether
  • alkene can be alternatively referred to as "olefin”; the term “linear” can be alternatively referred to as “normal”; and the term “isoolefin” can be alternatively referred to as "methyl branched isoolefin.”
  • olefin the term “alkene” can be alternatively referred to as "olefin”
  • linear can be alternatively referred to as "normal”
  • isoolefin can be alternatively referred to as "methyl branched isoolefin.”
  • butene and butylene refer to the same four carbon alkene
  • pentene and amylene refer to the same five carbon alkene.
  • the zeolite catalyst useful in the processes of this invention comprises a zeolite having a one-dimensional pore structure with a pore size ranging from greater than 0.42 nm and less than 0.7 nm.
  • the zeolite catalyst preferably comprises substantially only zeolites with the specified pore size in one dimension. Zeolites having pore sizes greater than 0.7 nm are susceptible to unwanted aromatization, oligimerization, alkylation, coking and by-product formation. Further, two or three-dimensional zeolites having a pore size greater than 0.42 nm in two or more dimensions permit dimerization and trimerization of the alkene.
  • zeolites having a pore diameter bigger than about 0.7 nm in any dimension or having a two or three-dimensional pore structure in which any two of the dimensions has a pore size greater than about 0.42 nm are excluded as part of this invention.
  • the specific zeolites that can be used in the processes of this invention are the hydrogen form of ferrierite and isotypic structures thereof, such as FU-9, NU-23 and ZSM-35.
  • the isotypic structures of these frameworks known under other names, are considered to be equivalent.
  • An overview describing the framework compositions of many of these zeolites is provided in New Developments in Zeolite Science Technology, "Aluminophosphate Molecular Sieves and the Periodic Table,” Hanigen et al. (Kodansha Ltd., Tokyo, Japan 1986).
  • zeolites such as ferrierite feature a one-dimensional pore structure with a pore size slightly smaller than the desired 0.42 nm diameter. These same zeolites can be converted to zeolites with larger pore sizes by removing the associated alkali metal or alkaline earth metal by methods known in the art, such as ammonium ion exchange, optionally followed by calcination, to yield the zeolite in its hydrogen form. See e.g. , U.S. Patent Nos. 4,795,623 and 4,942,027. Replacing the associated alkali or alkaline earth metal with the hydrogen form correspondingly enlarges the pore diameter.
  • the zeolite catalyst used in the isomerization processes of this invention can be used alone or suitably combined with a binder, typically a refractory oxide.
  • Suitable refractory oxides include natural clays, such as bentonite, montmorillonite, attapulgite, and kaolin; alumina; bentonite with alumina; silica; silica-alumina; hydrated alumina; titania; zirconia and mixtures thereof.
  • the weight ratio of binder material and zeolite suitably ranges from 1:9.5 to 9:1, preferably 1:4.
  • Catalytic compositions comprising the crystalline zeolite material of the invention and a suitable binder material can be formed by blending a finely divided crystalline zeolite with a binder material.
  • the resulting mixture can be thoroughly blended and mulled typically by adding water and/or a volatizable acidic material such as nitric acid or acetic acid.
  • the resulting gel can be dried and calcined, for example, at temperatures between 450°C and 550°C, preferably between 500°C and 520°C, to form a composition in which the crystalline zeolite is distributed throughout the matrix of binder material.
  • the catalyst composition can be extruded to form pellets, cylinders, or rings, or shaped into spheres, wagon wheels or polylobe structures.
  • H-ferrierite is the preferred zeolite catalyst for use in the isomerization processes of this invention.
  • H-ferrierite is derived from ferrierite, a naturally occurring zeolite mineral having a composition varying somewhat with the particular source.
  • a typical elemental composition of ferrierite is Na 2 Mg 2 [Al 6 Si 30 O 72 ] ⁇ 18 H 2 O.
  • ferrierite found by x-ray crystallography are parallel channels in the alumino-silicate framework. These channels, which are roughly elliptical in cross-section, are of two sizes: larger channels having major and minor axes of 5.4 and 4.2 ⁇ , respectively, and smaller parallel channels having major and minor axes of 4.8 and 3.5 ⁇ , respectively. Conversion of ferrierite to its hydrogen form, H-ferrierite, replaces sodium cations with hydrogen ions in the crystal structure. Both the alkali metal and hydrogen forms reject multiple branched chain and cyclic hydrocarbon molecules and retard coke formation.
  • H-ferrierite is considered to be comprised substantially of a one-dimensional pore structure having an elliptical pore size (> 0.54 nm and > 0.42 nm) large enough to permit entry of the linear olefin and diffusion of the methyl branched isoolefin and small enough to retard coke formation.
  • the one-dimensional feature is satisfied because there are no other interconnecting channels which have diameters similar to or greater than the primary (> 0.54 nm and > 0.42 nm) channel.
  • H-ferrierite will have a silica (SiO 2 ):alumina (Al 2 O 3 ) molar ratio from 42:1 to 100:1 or 300:1.
  • a hydrogen exchanged ferrierite powder with a molar silica (SiO 2 ) to alumina (Al 2 O 3 ) ratio of about 19, a sodium content less than 0.01 wt.% and a surface area of 420 square meters/gram was used to prepare the catalyst.
  • the framework of this zeolite contained both 8 and 10 T-atom rings arranged as described on pages 64 and 65, of the book "Atlas of Zeolite Structure Types" by W.M. Meier and D.H. Olson, Butterworths, 2nd Edition, 1987.
  • the pore dimensions of the 8 and 10 T-atom rings in this H-ferrierite are slightly larger than 3.5 ⁇ x 4.8 ⁇ (0.35 x 0.48nm) and 4.2 ⁇ x 5.4 ⁇ (0.42 x 0.54 nm), respectively.
  • the finished catalyst pore size distribution by mercury intrusion was bi-modal in nature with peaks at approximately 35 (3.5 nm) and 1150 angstroms (115 nm).
  • This H-ferrierite powder was extruded with alumina and calcined at 500°C to produce 1/16" (0.16 cm) cylinders of a H-ferrierite catalyst with the following measured physical properties.
  • the K/Na-ferrierite was converted into the ammonium form by ammonium ion exchange. After washing and drying, the NH 4 -ferrierite powder was pressed, crushed and sieved into 6-20 mesh particles. The particles were then calcined for two hours at 500°C.
  • 20 wt .% silica binder sica grade 951 obtained from W.R. Grace Co.
  • the mixture was pressed, crushed and sieved into 6-20 mesh particles.
  • the resulting particles exhibited a higher crush strength than the pressed zeolite material alone, i.e., H-ferrierite catalyst No. 2.
  • a hydrocarbon stream comprising a linear olefin is contacted with the catalytic zeolite under isomerizing conditions.
  • the hydrocarbon stream is contacted with the above-described zeolite catalyst in a vapor phase at a suitable reaction temperature, pressure and space velocity.
  • suitable reaction conditions include a temperature from 340°C to 600°C, an olefin partial pressure of above 0.5 atmosphere (50.66 kPa), and a total pressure of 0.5 to 10.0 atmospheres (1013 kPa) or higher, a hydrogen/hydrocarbon molar ratio of 0 to 30 or higher, substantially free of water (i.e., less than about 2.0 wt % of the feed), and a hydrocarbon weight hourly space velocity (WHSV) of 1.0 to 50 hr -1 .
  • the hydrogen can be added directly to the feed stream prior to introduction of the isomerization zone, or the hydrogen can be added directly to the isomerization zone.
  • an olefin-containing hydrocarbon vapor stream is contacted with such catalyst in a reactor at 340°C to 475°C, at an olefin partial pressure of 10 psia to 20 psia (69 to 138 kPa) and a total pressure of 15 to 30 psia (103 to 206 kPa), without added hydrogen, and at a hydrocarbon based WHSV of 2 to 28 hr -1 .
  • Preferred isomerizing conditions are carried out at a temperature of between 370°C to 440°C, at atmospheric pressures, and a hydrocarbon based WHSV of between 7 to 15 hr -1 .
  • the process according to the present invention can be carried out in a packed bed reactor, a fixed bed, fluidized bed reactor or a moving bed reactor.
  • the bed of the catalyst can move upward or downward.
  • the catalyst can be regenerated by subjecting it to heat treatment with air, nitrogen/oxygen gas mixture, or hydrogen.
  • a continuous regeneration similar to the regeneration carried out in a fluidized catalytic cracking process may be useful.
  • the performance of the zeolite catalyst can be affected by controlling the water content in the catalyst.
  • Water content of the catalyst can be adjusted by methods such as adding water to the feed or by directly adding water to the reactor. Calcination conditions will also affect the water content of the catalyst. These methods are referred to as controlled hydration of the catalyst.
  • the laboratory pilot unit was a semi-automated unit that can control flow, temperature, and pressure. It can also collect samples for analysis and record process variable data.
  • the process variable data was collected with an analog to digital (A to D) input/output converter.
  • the A to D converter was connected to a personal computer (PC) which runs a process control software package. This software package allowed the operator to monitor the process variable data and control the unit using proportional/integral/deri-vative (PID) control blocks for flow and pressure. It also archived the process variable data on magnetic media.
  • PC personal computer
  • the pilot reactor occupied three separate hoods:
  • the feed hood contained the feed system where the feed was stored in a five-gallon cylinder.
  • the feed tank rested on a load cell that was used to monitor the weight of the feed cylinder.
  • the feed tank was pressurized with a 60-80 psig (414 - 552 kPa.G) nitrogen blanket. This nitrogen pressure fed the hydrocarbon feed containing butylenes to the system.
  • the feed flow rate was controlled by PID control block in the process control software. This control block consisted of two flow meters, an instrument to pneumatic signal converter, and a flow control valve located downstream of the flow meters. The two flow meters were used independently and were calibrated for different flow rate ranges.
  • the feed system also had an additional connection for bottled gas addition or water injection with the feed.
  • the reactor hood contained the reactor and heating furnace.
  • the reactor was a 2 inch (5.1 cm) o.d. and 1.6 inch (4.1 cm) i.d. stainless steel pipe with 2-inch flanges welded to each end.
  • the pipe also had 1/4 inch (0.65 cm) feed and effluent lines welded on 6 inches (15 cm) from the bottom and top of the reactor respectively.
  • the top sealing flange was fitted with a pressure gauge and rupture disk.
  • the bottom sealing flange had a thermocouple well welded directly in the center of the flange that extends up through the middle of the reactor pipe when attached.
  • the thermocouple well was a 1/2 inch (1.3 cm) stainless steel tube welded shut at one end and contained eight or more thermocouple points.
  • the reactor pipe was enclosed with a Lindberg three foot (0.91 m) heating furnace containing three heating zones but only the bottom zone was used to preheat the butylene feed to the reaction section.
  • the furnace was controlled by three controllers comprising a PID control block for monitoring and controlling the temperature inside the reactor at each zone.
  • Located on the effluent line was tubing and equipment for the sampling system.
  • the sampling system included an air actuated valve and a steam traced line of helium that carried the sample to the gas chromatograph (GC) for direct injection.
  • GC gas chromatograph
  • the product hood contained the effluent cooler, the condensables collection tank, and the effluent pressure transmitter.
  • the effluent condenser consisted of a coiled tube that contained the effluent line as the inner tube. Cooling water flowed through the outer tube to cool the effluent containing inner tube. Downstream of the condenser was the 5 gallon (18.9 litres) condensables collection tank.
  • the effluent pressure was controlled by a PID control block in the process control software. This control block consisted of a pressure transducer (located upstream of the condenser), an instrument to pneumatic signal converter, and a pressure control valve (located downstream of the collection tank). A vent for the noncondensables was located downstream of the pressure valve.
  • 1-pentene was pressurized with nitrogen in a 4-liter feed tank to about 60 psig (414 kPa.G) and then fed to reactor consisting of a stainless steel tube with inside diameter of 1 inch (2.5 cm).
  • Flow to the reactor was controlled with a mass flow controller, positive-displacement flow meter and control valve.
  • the outside of the reactor was heated with three Glas-Col heating mantles with corresponding, temperature controllers. Feed was introduced into the top of the reactor through 1/4 inch (0.65 cm) feed lines with tubing connections.
  • a thermowell in the bottom of the reactor contained six thermocouples to measure temperature at various points in the reactor.
  • a refrigerated circulating bath with shell and tube heat exchanger was used to condense the vapors from the reactor at atmospheric pressure.
  • liquid samples are collected in a cooled 1-liter stainless steel sample bomb and then analyzed on an external gas chromatograph with alumina plot column. Small amounts of gaseous product were vented through a small bubble meter used to monitor flow. Samples of this gaseous product were collected in gas sample bags, analyzed and included in the final product analysis.
  • the liquid reaction products were analyzed using a Sigma gas chromatograph through a J&W alumina-plot column utilizing a flame ionization detector.
  • Gaseous samples were analyzed using a Hach gas chromatograph through a multi-column system utilizing both a thermal conductivity detector and flame ionization detector.
  • the reactor was first loaded with an inert packing material in the preheating zone.
  • the inert packing materials used were either a small mesh corundum or inert clay catalyst support balls.
  • the inert bed depth varied depending on the thermo-couple points the catalyst was to occupy.
  • a typical loading depth was about 30 inches (0.76 m) of inert material.
  • Above the packing material a weighed amount of catalyst is added to coincide with thermocouple points for reading temperature during the experiment.
  • the amount of catalyst used for the test varied depending on the weight hourly space velocity desired and the flow rates attainable with our equipment.
  • a typical loading consisted of 97 grams of catalyst which corresponded to a loading of about 4 inches (10 cm) in the reactor. Above the catalyst another layer of packing material was added to form a distinct zone of catalyst.
  • feed stream used was an MTBE processing effluent and comprised about 30-50% butene-2, 25-45% butene-1, and 20-30% n-butane.
  • the other feed stream used for testing comprised about 90% butene-2 and 9% butene-1 (termed herein "butylenes feed”).
  • Testing began by warming up the reactor to a minimum operating temperature usually greater than 200°C. The warming step was performed under a nitrogen purge of approximately 15-50 psia (103 - 305 kPa). Once the reactor was warmed, the flow control valve was opened to introduce feed to the reactor, and the nitrogen purge was turned off. WHSVs varied from 1 to 30 during the testing. The operating temperatures used for the testing varied in a range from 200°C to 550°C and depended on many factors, including the activity of the catalyst. The pressures used during the testing varied in response to restriction from the catalyst and reactor. Most all of the testing was performed with the pressure control valve open to the atmosphere. The recorded values of the effluent pressure, however, were in a range of about 15-45 psia (103 - 310 kPa).
  • Samples of the reactor effluent were manually sampled using the sampling system and gas chromatography. Sampling was performed manually rather than on an automatic specific time interval in order to have specific operating conditions for the process variables. The analysis was performed with a boiling point separation column or an alumina column.
  • Conversion and selectivity are calculated for each sample during testing runs and used for comparison of the various catalysts. It is believed that during the isomerization an equilibrium is achieved between butene-1 and trans and cis butene-2. Therefore the calculation of conversion and selectivity reflect the feed (FD) and effluent (EFF) concentrations of butene-1 (B1) and butene-2 (B2) and isobutylene (IB1).
  • % Conversion ( wt % B1 + wt % B2)FD - ( wt % B1 + wt % B2)EFF ( wt % B1 + wt % B2)FD X
  • Examples 6-26 feature data illustrating isobutylene conversion using an MTBE processing effluent feed.
  • the testing apparatus and procedure were the same as described above.
  • FIG. 1 is a graph of the conversion and selectivity wt % versus run time depicting the results of this example.
  • FIG. 2 is a graph of isobutylene yield and isobutylene wt % versus run time for the results of this example.
  • FIG. 3 is a graph of the conversion and selectivity wt % versus run time depicting the results of this example.
  • FIG. 4 is a graph of isobutylene yield and isobutylene wt % versus run time for the results of this example.
  • FIG. 5 is a graph of the conversion and selectivity wt % versus run time depicting the results of this example.
  • FIG. 6 is a graph of isobutylene yield and isobutylene wt % over run time for the results of this example.
  • Examples 22-24 show experimental results using the larger pore hydrogen mordenite.
  • Examples 25 and 26 show experimental results reflecting improved results of isobutylene selectivities using the smaller pore magnesium mordenite.
  • Examples 27-29 show experimental results of isopentene conversion using a 1-pentene feed.
  • the testing apparatus and procedure were the same as described earlier for the n-pentene stream.
  • FIG. 7 depicts a flow scheme for producing an alkyl-tert-alkyl-ether, particularly methyl-tert-butyl-ether (MTBE) by means of first isomerizing n-butene to isobutylene, separating out an isobutylene stream for further processing to produce MTBE.
  • a hydrocarbon stream containing butylene is charged to an isomerization zone 4, via conduit 2.
  • the hydrocarbon stream can be charged continuously.
  • the isomerization zone 4 contains an isomerizing catalyst, preferably the hydrogen form of ferrierite.
  • the isomerization zone is further maintained at isomerizing conditions so as to maximize the structural isomerization of butylene to isobutylene.
  • the effluent from the isomerization zone 4 containing isobutylene is passed through conduit 6 to a separation zone 8.
  • the isomerizing catalyst can be regenerated in the isomerization zone 4.
  • the separation zone 8 is maintained under conditions sufficient to maximize separation of isobutylene from the lighter olefins, ethylene and propylene, and from the heavier olefins, aromatics and paraffins.
  • the separation zone 8 can employ various means known in the art to effect separation of light, medium and heavy olefins, aromatics or paraffins.
  • the zone may comprise a series of adsorbent beds comprising molecular sieves as described in U.S. Patent Nos. 4,717,784 and 4,210,771, incorporated herein by reference.
  • the separation zone may conveniently separate the light, medium and heavy fractions by distillation using processes well known in the art.
  • the lighter olefins, ethylene and propylene, and lighter paraffins are removed via conduit 10.
  • the higher paraffins and olefins, C 5 and above, and aromatics are removed via conduit 12.
  • the butylene fraction, comprising isobutylene, is removed from the separation zone via conduit 14 to an MTBE reaction zone 16 containing an etherification catalyst. Thereafter, methanol is fed into the MTBE reaction zone 16 via conduit 18.
  • the MTBE reaction process can be carried out in any one of a number of ways, such as for example taught by U.S. Patent No. 4,876,394, incorporated herein by reference.
  • the MTBE effluent 20 is recovered preferably as a bottoms product and the unreacted butene/isobutylene stream is recovered and recycled via conduit 22 to the butylene feed at conduit 2.

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Claims (13)

  1. Verfahren zur strukturellen Isomerisierung eines linearen C4- bis C10-Olefins in ein Methyl-verzweigtes lsoolefin, welches das Zusammenbringen des Olefins mit einem Katalysator, umfassend die Wasserstoff-Form von Ferrierit oder einer typengleichen Struktur davon, mit einem Siliciumdioxid/Aluminiumoxid-Verhältnis von 42:1 bis 300:1, bei lsomerisationsbedingungen, umfassend eine Temperatur von 340°C bis 600°C, einen Ofefin-Partialdruck von über 0,5 Atmosphären (50,66 kPa) und eine Raumgeschwindigkeit in Stunden des Kohlenwasserstoff-Gewichts (hydrocarbon weight hour space velocity) von 1 bis 50 hr-1, umfaßt.
  2. Verfahren nach Anspruch 1, wobei das lineare Olefin mindestens eines von 1-Buten, cis-2-Buten, trans-2-Buten, 1-Penten, cis-2-Penten und trans-2-Penten ist.
  3. Verfahren nach Anspruch 1 oder 2, wobei der Kohlenwasserstoff-Zulauf 40 bis 100 Gew.-% normales Buten oder normales Penten umfaßt.
  4. Verfahren nach einem der vorangehenden Ansprüche, wobei das Zeolit mit einem Bindemittel kombiniert wird.
  5. Verfahren nach Anspruch 4, wobei das Bindemittel mindestens eines von Siliciumdioxid, Siliciumdioxid-Aluminiumoxid, Bentonit, Kaolin, Bentonit mit Aluminiumoxid, Montmorillonit, Attapulgit, Titaniumdioxid und Zirkoniumdioxid ist.
  6. Verfahren nach einem der vorangehenden Ansprüche, wobei die Temperatur 340°C bis 475°C beträgt.
  7. Verfahren nach einem der vorangehenden Ansprüche, wobei die Temperatur mindestens 370°C beträgt.
  8. Verfahren nach einem der vorangehenden Ansprüche, wobei die Temperatur mindestens 400°C beträgt.
  9. Verfahren nach einem der vorangehenden Ansprüche, wobei die Temperatur 400°C bis 440°C beträgt.
  10. Verfahren nach einem der vorangehenden Ansprüche, wobei der Katalysator ZSM-35, FU-9 oder NU-23 umfaßt.
  11. Verfahren nach einem der vorangehenden Ansprüche, wobei die Raumgeschwindigkeit in Stunden des Kohlenwasserstoff-Gewichts mindestens 7 hr-1 beträgt.
  12. Verfahren nach einem der vorangehenden Ansprüche, welches die folgenden weiteren Schritte umfaßt:
    (i) Weiterleiten des Ablaufs aus der Isomerisierung zu einer Veretherungszone, enthaltend einen Alkohol und einen Veretherungs-Katalysator, zum Erhalt eines Reaktionsprodukts, umfassend einen Alkyl-tert-Alkylether, und
    (ii) Rückgewinnen des Alkyl-tert-Alkylether-Reaktionsprodukts.
  13. Verfahren nach Anspruch 12, wobei die lsomerisierungszone einen Festbettreaktor, Bewegtbettreaktor oder Flüssigbettreaktor umfaßt.
EP92305090A 1991-06-05 1992-06-03 Verfahren zur Isomerisierung von geradlinigen Olefinen in Isoolefine Expired - Lifetime EP0523838B9 (de)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US71104191A 1991-06-05 1991-06-05
US07/711,044 US6323384B1 (en) 1991-06-05 1991-06-05 Process for isomerizing linear olefins to isoolefins
US711041 1991-06-05
US711044 1991-06-05
US87433592A 1992-04-24 1992-04-24
US874335 1992-04-24

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NO922209D0 (no) 1992-06-04
EP0523838A3 (en) 1993-08-04
EP0523838A2 (de) 1993-01-20
FI922581A0 (fi) 1992-06-04
SG67315A1 (en) 1999-09-21
ES2138964T3 (es) 2000-02-01
DE69229980T2 (de) 2000-01-05
AU1805292A (en) 1993-03-11
ATE184586T1 (de) 1999-10-15
AU3310295A (en) 1995-12-07
RU2127717C1 (ru) 1999-03-20
JP3195413B2 (ja) 2001-08-06
MX9202721A (es) 1992-12-01
NO922209L (no) 1992-12-07
CA2070595A1 (en) 1992-12-06
NO307655B1 (no) 2000-05-08
DE69229980D1 (de) 1999-10-21
FI110608B (fi) 2003-02-28
EP0523838B1 (de) 1999-09-15
CA2070595C (en) 2004-11-23
FI922581A (fi) 1992-12-06

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